CN103771527A - Bi0.92Dy0.08Fe(1-x)MnxO3 ferroelectric film with low coercive field and preparation method of film - Google Patents
Bi0.92Dy0.08Fe(1-x)MnxO3 ferroelectric film with low coercive field and preparation method of film Download PDFInfo
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- CN103771527A CN103771527A CN201310714217.4A CN201310714217A CN103771527A CN 103771527 A CN103771527 A CN 103771527A CN 201310714217 A CN201310714217 A CN 201310714217A CN 103771527 A CN103771527 A CN 103771527A
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Abstract
The invention discloses a Bi0.92Dy0.08Fe(1-x)MnxO3 ferroelectric film with a low coercive field and a preparation method of the film. In Bi0.92Dy0.08Fe(1-x)MnxO3, x is 0.01-0.05; the film is of a rhombohedral structure and is good in uniformity; the residual polarization intensity is 58.27-69.87 muC/cm<2>; the coercive field is 318-448kV/cm; the dielectric constant is 214.4-260.6. The preparation method comprises the following steps: dissolving bismuth nitrate, ferric nitrate, dysprosium nitrate and manganese acetate into a mixed solution prepared from ethylene glycol monomethyl ether and acetic oxide in a mixing manner, so as to obtain a precursor solution; spinning the precursor solution on a substrate; baking after spinning to obtain a dry film; annealing to obtain the Bi0.92Dy0.08Fe(1-x)MnxO3 film; repeatedly spinning the precursor solution, baking and annealing to achieve the required film thickness, so as to obtain the film. According to the invention, equipment requirements are simple, doping content is easy to control, and the ferroelectric properties of the BiFeO3 film can be greatly improved.
Description
Technical field
The invention belongs to field of functional materials, be specifically related to a kind of Bi of low coercive field
0.92dy
0.08fe
1-xmn
xo
3ferroelectric membranc and preparation method thereof.
Background technology
As the typical single-phase multiferroic perovskite material of one, BiFeO
3that minority at room temperature has ferroelectricity (Curie temperature T simultaneously
c～1023K) and ferromegnetism (Neel temperature T
n～643K) one of material, have potential application prospect at aspects such as message memory, spin electric device, sensor and MEMS (micro electro mechanical system).At present for the preparation of BiFeO
3the method of film has a lot, has chemical Vapor deposition process (CVD), magnetron sputtering method (rf magnetron sputtering), deposition of metal organic method (MOD), metal-organic chemical vapor deposition equipment method (MOCVD), liquid phase deposition (LPD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD), sol-gel method (Sol-Gel) etc.But, the BiFeO that utilizes metal-organic decomposition method to prepare
3film leakage current is higher, and coercive field is larger, magnetic a little less than, and only in the time that thickness is greater than 400nm, just can observe saturated P-E ferroelectric hysteresis loop.Therefore in order to meet the requirement of following microelectronic device, reduce BiFeO
3leakage current, coercive field and the thickness of-base film, and the ferroelectric and ferromagnetic property of raising film is current several key issues urgently to be resolved hurrily.
Summary of the invention
The object of the present invention is to provide a kind of Bi of low coercive field
0.92dy
0.08fe
1-xmn
xo
3ferroelectric membranc and preparation method thereof, the method equipment requirements is simple, and experiment condition easily reaches, and the uniformity of film of preparation is better, and doping is easily controlled, and can increase substantially ferroelectric properties and the dielectric properties of film.
To achieve these goals, the present invention adopts following technical scheme:
A kind of Bi of low coercive field
0.92dy
0.08fe
1-xmn
xo
3ferroelectric membranc, its chemical formula is Bi
0.92dy
0.08fe
1-xmn
xo
3, x=0.01～0.05; Under 1kHz frequency, its remnant polarization is 58.27～69.87 μ C/cm
2, coercive field is 318～448kV/cm, specific inductivity is 214.4～260.6.
It is water chestnut square structure, and space group is R-3m (166), unit cell parameters
grain size is 30～80nm.
Comprise Bi
0.92dy
0.08fe
0.99mn
0.01o
3ferroelectric membranc, Bi
0.92dy
0.08fe
0.98mn
0.02o
3ferroelectric membranc, Bi
0.92dy
0.08fe
0.97mn
0.03o
3ferroelectric membranc and Bi
0.92dy
0.08fe
0.95mn
0.05o
3ferroelectric membranc;
And Bi
0.92dy
0.08fe
0.99mn
0.01o
3ferroelectric membranc is under the electric field of 583kV/cm, and remnant polarization is 63.62 μ C/cm
2, coercive field is 318kV/cm, in 1kHz～1MHz range of frequency, specific inductivity is 243.1～206.6;
Bi
0.92dy
0.08fe
0.98mn
0.02o
3ferroelectric membranc is under the electric field of 833kv/cm, and remnant polarization is 69.87 μ C/cm
2, coercive field is 330kv/cm, in 1kHz～1MHz range of frequency, specific inductivity is 260.6～220.69;
Bi
0.92dy
0.08fe
0.97mn
0.03o
3ferroelectric membranc is under the electric field of 833kV/cm, and remnant polarization is 58.27 μ C/cm
2, coercive field is 343kV/cm, in 1kHz～1MHz range of frequency, specific inductivity is 214.4～167.01;
Bi
0.92dy
0.08fe
0.95mn
0.05o
3ferroelectric membranc is under the electric field of 917kV/cm, and remnant polarization is 62.88 μ C/cm
2, coercive field is 448kV/cm, in 1kHz～1MHz range of frequency, specific inductivity is 232.3～164.76.
The Bi of low coercive field
0.92dy
0.08fe
1-xmn
xo
3the preparation method of ferroelectric membranc, comprises the following steps:
Step 1: be 0.97:(1-x in molar ratio): 0.08:x is by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Dy (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in the mixed solution being mixed by ethylene glycol monomethyl ether and acetic anhydride, stirs, and obtains precursor liquid; Wherein, in precursor liquid, total concentration of metal ions is 0.25～0.35mol/L, x=0.01～0.05;
Step 2: precursor liquid is spin-coated on FTO/glass substrate and prepares wet film, and wet film toasts to obtain dry film after even glue at 180～210 ℃, then 540～550 ℃ of annealing, obtains Bi
0.92dy
0.08fe
1-xmn
xo
3film;
Step 3: treat Bi
0.92dy
0.08fe
1-xmn
xo
3after film cooling, then at Bi
0.92dy
0.08fe
1-xmn
xo
3on film, repeating step 2, makes Bi
0.92dy
0.08fe
1-xmn
xo
3film reaches desired thickness, obtains the Bi of low coercive field
0.92dy
0.08fe
1-xmn
xo
3ferroelectric membranc.
In described step 1, in mixed solution, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5～3.5): 1.
X=0.01,0.02,0.03 or 0.05 in described step 1.
In described step 2, first FTO/glass substrate is cleaned, dried, then radiation treatment under UV-light, makes FTO/glass substrate surface reach atomic cleanliness degree, finally spin coating precursor liquid again.
Even glue speed in described step 2 when even glue is 3800～4100r/min, and the even glue time is 12～15s.
Baking time in described step 2 after even glue is 8～12min.
In described step 2, annealing time is 7～9min.
With respect to prior art, the present invention has following beneficial effect:
The invention provides a kind of Bi of low coercive field
0.92dy
0.08fe
1-xmn
xo
3the preparation method of ferroelectric membranc, adopts sol-gel method, by A position Dy and B position Mn codoped, prepares the Bi of low coercive field at FTO/glass substrate surface
0.92dy
0.08fe
1-xmn
xo
3ferroelectric membranc.The method selects lanthanon Dy to carry out the doping of A position, at BiFeO
3a position doping lanthanon can stablize the iron oxygen octahedra in perovskite structure, simultaneously because Dy has substituted part Bi, the volatile quantity of Bi in annealing process reduced, thereby reduced the generation in oxygen room, can make Bi
0.92dy
0.08fe
1-xmn
xo
3the insulativity of ferroelectric membranc effectively strengthens, and reduces leakage conductance.In addition, the present invention also selects Mn to carry out the doping of B position, and the doping of B position can improve BiFeO equally effectively
3the multi-ferrum property of film.Because the Mn selecting is+divalent, so at alternative Fe
3+time can reduce the generation in oxygen room because of charge compensation effect, thereby can effectively reduce leakage current.Simultaneously to B position Fe
3+substituting of ion can affect the magnetic structure of its crystal grain inside consumingly, and then affects its magnetic and magnetoelectric effect.And these two kinds of ions mix altogether that can to make membrane structure be R-3m (166) spacer of water chestnut square structure.So that the present invention adopts is the Bi that the ion co-doped method of A position rare earth ion and B position magnetic transition metal (i.e. so-called " compound substituting ") is prepared low coercive field
0.92dy
0.08fe
1-xmn
xo
3ferroelectric membranc.This method can be taken into account the advantage of two kinds of substitute element, replaces and partly overcome single element of planting the shortcoming of bringing, and makes BiFeO
3ferroelectric properties be able to more significantly improve.And compare additive method, the sol-gel method equipment requirements that the present invention adopts is simple, do not need expensive vacuum apparatus, experiment condition easily reaches, reaction is easily carried out, temperature of reaction is lower, be conducive to solve the problem that Fe appraises at the current rate and Bi volatilizees in film preparation process, simultaneously suitablely on large surface and surface in irregular shape, prepare film, easy handling and doping vario-property, can effectively control component and the structure of film, film chemical composition is accurately controlled, doping is easily controlled, be particularly suitable for preparing multicomponent oxide film material, can accurately control the stoichiometric ratio of film, be easy to realize the Uniform Doped on molecular level.
The Bi of the low coercive field that the present invention makes
0.92dy
0.08fe
1-xmn
xo
3ferroelectric membranc (x=0.01～0.05) is water chestnut square structure, and space group is R-3m (166), unit cell parameters
grain size is 30～80nm, good uniformity, and under 1kHz frequency, its remnant polarization is 58.27～69.87 μ C/cm
2, coercive field is 318～448kV/cm, specific inductivity is 214.4～260.6, has increased substantially BiFeO
3the ferroelectric properties of film and dielectric properties.
Accompanying drawing explanation
Fig. 1 is different Mn
2+the Bi preparing under doping
0.92dy
0.08fe
1-xmn
xo
3the XRD spectra of ferroelectric membranc, wherein a is the Bi making according to preparation method of the present invention
0.92dy
0.08feO
3the XRD spectra of ferroelectric membranc, b～e is respectively the Bi that embodiment 1～embodiment 4 prepares
0.92dy
0.08fe
1-xmn
xo
3the XRD spectra of ferroelectric membranc;
Fig. 2 is different Mn
2+the Bi preparing under doping
0.92dy
0.08fe
1-xmn
xo
3the SEM figure of ferroelectric membranc, wherein (a)～(d) is respectively the Bi that embodiment 1～embodiment 4 prepares
0.92dy
0.08fe
1-xmn
xo
3the SEM figure of ferroelectric membranc;
Fig. 3 is different Mn
2+the Bi preparing under doping
0.92dy
0.08fe
1-xmn
xo
3the specific inductivity figure of ferroelectric membranc, wherein a is the Bi making according to preparation method of the present invention
0.92dy
0.08feO
3the specific inductivity figure of ferroelectric membranc, b～e is respectively the Bi that embodiment 1～embodiment 4 prepares
0.92dy
0.08fe
1-xmn
xo
3the specific inductivity figure of ferroelectric membranc;
Fig. 4 is different Mn
2+the Bi preparing under doping
0.92dy
0.08fe
1-xmn
xo
3the ferroelectric hysteresis loop figure of ferroelectric membranc, wherein a is the Bi making according to preparation method of the present invention
0.92dy
0.08feO
3the ferroelectric hysteresis loop figure of ferroelectric membranc, b～e is respectively the Bi that embodiment 1～embodiment 4 prepares
0.92dy
0.08fe
1-xmn
xo
3the ferroelectric hysteresis loop figure of ferroelectric membranc.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment 1
Step 1: in molar ratio for 0.97:0.99:0.08:0.01(is x=0.01) by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Dy (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in mixed solution, obtains even, stable precursor liquid after magnetic agitation 2.5h, and wherein mixed solution is to be 3:1 by volume ratio ethylene glycol monomethyl ether and acetic anhydride mix, and in precursor liquid, total concentration of metal ions is 0.3mol/L;
Step 2: first FTO/glass substrate is cleaned, dried, then radiation treatment under UV-light, make FTO/glass substrate surface reach atomic cleanliness degree, adopt again spin-coating method spin coating precursor liquid on FTO/glass substrate to prepare wet film, with the even glue 12s of even glue speed of 4000r/min, after even cementing bundle, at 200 ℃, toast 10min and obtain dry film, then at 550 ℃ of short annealing 9min, obtain Bi
0.92dy
0.08fe
0.99mn
0.01o
3film;
Step 3: treat Bi
0.92dy
0.08fe
0.99mn
0.01o
3after film cooling, then at Bi
0.92dy
0.08fe
0.99mn
0.01o
3on film, repeating step 2, makes Bi
0.92dy
0.08fe
0.99mn
0.01o
3film reaches desired thickness, obtains the Bi of low coercive field
0.92dy
0.08fe
0.99mn
0.01o
3ferroelectric membranc.
At the Bi of low coercive field
0.92dy
0.08fe
0.99mn
0.01o
30.502mm is prepared in the sputter of ferroelectric membranc surface ion
2au electrode, then 295 ℃ insulation 20min electrode is contacted completely with substrate.Adopt the Bi of the low coercive field of XRD determining
0.92dy
0.08fe
0.99mn
0.01o
3the thing phase composite structure of ferroelectric membranc, as shown in Figure 1 b, the Bi of low coercive field
0.92dy
0.08fe
0.99mn
0.01o
3ferroelectric membranc diffraction peak and standard P DF card: 86-1518 matches, be water chestnut square structure, and space group is R-3m (166), unit cell parameters
measure the Bi of low coercive field with FE-SEM
0.92dy
0.08fe
0.99mn
0.01o
3the microscopic appearance of ferroelectric membranc, as shown in Fig. 2 (a), its even grain size, size is 50～80nm, has a small amount of pore in film; With the Bi of the low coercive field of the ferroelectric test system and test of TF2000
0.92dy
0.08fe
0.99mn
0.01o
3the ferroelectric properties of ferroelectric membranc, as shown in Figure 4 b, under the electric field of 583kV/cm, under 1kHz frequency, its remnant polarization is 63.62 μ C/cm
2, coercive field is 318kV/cm; Test the Bi of low coercive field with Agilent E4980A LCR test set
0.92dy
0.08fe
0.99mn
0.01o
3the dielectric properties of ferroelectric membranc, as shown in Figure 3 b, within the scope of 1kHz～1MHz test frequency, its specific inductivity is 243.1～206.6.
Embodiment 2
Step 1: in molar ratio for 0.97:0.98:0.08:0.02(is x=0.02) by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Dy (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in mixed solution, obtains even, stable precursor liquid after magnetic agitation 2.5h, and wherein mixed solution is to be 3:1 by volume ratio ethylene glycol monomethyl ether and acetic anhydride mix, and in precursor liquid, total concentration of metal ions is 0.3mol/L;
Step 2: first FTO/glass substrate is cleaned, dried, then radiation treatment under UV-light, make FTO/glass substrate surface reach atomic cleanliness degree, adopt again spin-coating method spin coating precursor liquid on FTO/glass substrate to prepare wet film, with the even glue 12s of even glue speed of 4000r/min, after even cementing bundle, at 200 ℃, toast 10min and obtain dry film, then at 550 ℃ of short annealing 9min, obtain Bi
0.92dy
0.08fe
0.98mn
0.02o
3film;
Step 3: treat Bi
0.92dy
0.08fe
0.98mn
0.02o
3after film cooling, then at Bi
0.92dy
0.08fe
0.98mn
0.02o
3on film, repeating step 2, makes Bi
0.92dy
0.08fe
0.98mn
0.02o
3film reaches desired thickness, obtains the Bi of low coercive field
0.92dy
0.08fe
0.98mn
0.02o
3ferroelectric membranc.
At the Bi of low coercive field
0.92dy
0.08fe
0.98mn
0.02o
30.502mm is prepared in the sputter of ferroelectric membranc surface ion
2au electrode, then 295 ℃ insulation 20min electrode is contacted completely with substrate.Adopt the Bi of the low coercive field of XRD determining
0.92dy
0.08fe
0.98mn
0.02o
3the thing phase composite structure of ferroelectric membranc, as shown in Fig. 1 c, the Bi of low coercive field
0.92dy
0.08fe
0.98mn
0.02o
3the diffraction peak of ferroelectric membranc and standard P DF card: 86-1518 matches, be water chestnut square structure, and space group is R-3m (166), unit cell parameters
measure the Bi of low coercive field with FE-SEM
0.92dy
0.08fe
0.98mn
0.02o
3the microscopic appearance of ferroelectric membranc, as shown in Fig. 2 (b), its grain size is about 40～70nm, and film is dense; With the Bi of the low coercive field of the ferroelectric test system and test of TF2000
0.92dy
0.08fe
0.98mn
0.02o
3the ferroelectric properties of ferroelectric membranc, as shown in Fig. 4 c, under the test electric field of 833kV/cm, under 1kHz frequency, recording its remnant polarization is 69.87 μ C/cm
2, coercive field is 330kV/cm; With Agilent E4980A LCR test set test b i
0.92dy
0.08fe
0.98mn
0.02o
3the dielectric properties of ferroelectric membranc, as shown in Figure 3 c, within the scope of 1kHz～1MHz test frequency, its specific inductivity is 260.6～220.9.
Embodiment 3
Step 1: in molar ratio for 0.97:0.97:0.08:0.03(is x=0.03) by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Dy (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in mixed solution, obtains even, stable precursor liquid after magnetic agitation 2.5h, and wherein mixed solution is to be 3:1 by volume ratio ethylene glycol monomethyl ether and acetic anhydride mix, and in precursor liquid, total concentration of metal ions is 0.3mol/L;
Step 2: first FTO/glass substrate is cleaned, dried, then radiation treatment under UV-light, make FTO/glass substrate surface reach atomic cleanliness degree, adopt again spin-coating method spin coating precursor liquid on FTO/glass substrate to prepare wet film, with the even glue 12s of even glue speed of 4000r/min, after even cementing bundle, at 200 ℃, toast 10min and obtain dry film, then at 550 ℃ of short annealing 9min, obtain Bi
0.92dy
0.08fe
0.97mn
0.03o
3film;
Step 3: treat Bi
0.92dy
0.08fe
0.97mn
0.03o
3after film cooling, then at Bi
0.92dy
0.08fe
0.97mn
0.03o
3on film, repeating step 2, makes Bi
0.92dy
0.08fe
0.97mn
0.03o
3film reaches desired thickness, obtains the Bi of low coercive field
0.92dy
0.08fe
0.97mn
0.03o
3ferroelectric membranc.
At the Bi of low coercive field
0.92dy
0.08fe
0.97mn
0.03o
30.502mm is prepared in the sputter of ferroelectric membranc surface ion
2au electrode, then 295 ℃ insulation 20min electrode is contacted completely with substrate.Adopt the Bi of the low coercive field of XRD determining
0.92dy
0.08fe
0.97mn
0.03o
3the thing phase composite structure of ferroelectric membranc, as shown in Figure 1 d, the Bi of low coercive field
0.92dy
0.08fe
0.97mn
0.03o
3the diffraction peak of ferroelectric membranc and standard P DF card: 86-1518 matches, be water chestnut square structure, and space group is R-3m (166), unit cell parameters
measure the Bi of low coercive field with FE-SEM
0.92dy
0.08fe
0.97mn
0.03o
3the microscopic appearance of ferroelectric membranc, as shown in Fig. 2 (c), its grain size is about 40～70nm, occurs pore in film; With the Bi of the low coercive field of the ferroelectric test system and test of TF2000
0.92dy
0.08fe
0.97mn
0.03o
3the ferroelectric properties of ferroelectric membranc, as shown in Fig. 4 d, under the test electric field of 833kV/cm, under 1kHz frequency, recording its remnant polarization is 58.27 μ C/cm
2, coercive field is 343kV/cm; Test the Bi of low coercive field with Agilent E4980A LCR test set
0.92dy
0.08fe
0.97mn
0.03o
3the dielectric properties of ferroelectric membranc, as shown in Figure 3 d, within the scope of 1kHz～1MHz test frequency, its specific inductivity is 214.4～167.01.
Embodiment 4
Step 1: in molar ratio for 0.97:0.95:0.08:0.05(is x=0.05) by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Dy (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in mixed solution, obtains even, stable precursor liquid after magnetic agitation 2.5h, and wherein mixed solution is to be 3:1 by volume ratio ethylene glycol monomethyl ether and acetic anhydride mix, and in precursor liquid, total concentration of metal ions is 0.3mol/L;
Step 2: first FTO/glass substrate is cleaned, dried, then radiation treatment under UV-light, make FTO/glass substrate surface reach atomic cleanliness degree, adopt again spin-coating method spin coating precursor liquid on FTO/glass substrate to prepare wet film, with the even glue 12s of even glue speed of 4000r/min, after even cementing bundle, at 200 ℃, toast 10min and obtain dry film, then at 550 ℃ of short annealing 9min, obtain Bi
0.92dy
0.08fe
0.95mn
0.05o
3film;
Step 3: treat Bi
0.92dy
0.08fe
0.95mn
0.05o
3after film cooling, then at Bi
0.92dy
0.08fe
0.95mn
0.05o
3on film, repeating step 2, makes Bi
0.92dy
0.08fe
0.95mn
0.05o
3film reaches desired thickness, obtains the Bi of low coercive field
0.92dy
0.08fe
0.95mn
0.05o
3ferroelectric membranc.
At the Bi of low coercive field
0.92dy
0.08fe
0.95mn
0.05o
30.502mm is prepared in the sputter of ferroelectric membranc surface ion
2au electrode, then 295 ℃ insulation 20min electrode is contacted completely with substrate.Adopt the Bi of the low coercive field of XRD determining
0.92dy
0.08fe
0.95mn
0.05o
3the thing phase composite structure of ferroelectric membranc, as shown in Fig. 1 e, the Bi of low coercive field
0.92dy
0.08fe
0.95mn
0.05o
3the diffraction peak of ferroelectric membranc and standard P DF card: 86-1518 matches, be water chestnut square structure, and space group is R-3m (166), unit cell parameters
measure the Bi of low coercive field with FE-SEM
0.92dy
0.08fe
0.95mn
0.05o
3the microscopic appearance of ferroelectric membranc, as shown in Fig. 2 (d), its grain size is about 30～50nm, occurs a large amount of pores and defects i.e.cracks in film; With the ferroelectric test system and test Bi of TF2000
0.92dy
0.08fe
0.95mn
0.05o
3the ferroelectric properties of ferroelectric membranc, as shown in Fig. 4 e, under the test electric field of 917kV/cm, under 1kHz frequency, recording its remnant polarization is 62.88 μ C/cm
2, coercive field is 448kV/cm; With Agilent E4980A LCR test set test b i
0.92dy
0.08fe
0.95mn
0.05o
3the dielectric properties of ferroelectric membranc, as shown in Figure 3 e, within the scope of 1kHz～1MHz test frequency, its specific inductivity is 232.3～164.76.
Fig. 1 is different Mn
2+the Bi preparing under doping
0.92dy
0.08fe
1-xmn
xo
3the XRD figure spectrum of ferroelectric membranc, wherein a is according to preparation method of the present invention, does not add C in step 1
4h
6mnO
44H
2the Bi making when O
0.92dy
0.08feO
3the XRD figure spectrum of ferroelectric membranc: b～e is respectively the Bi that embodiment 1～embodiment 4 prepares
0.92dy
0.08fe
1-xmn
xo
3the XRD figure spectrum of ferroelectric membranc.In Fig. 1, the a.u. of unit of ordinate zou represents that it is arbitrary unit, and X-coordinate 2 θ are angle of diffraction.As can be seen from Figure 1 Bi
0.92dy
0.08fe
1-xmn
xo
3the diffraction peak of ferroelectric membranc (104) and (110) crystal face, along with the skew of turning left gradually that is increased in of doping, illustrates that variation has occurred film internal structure.
Fig. 2 is different Mn
2+the Bi preparing under doping
0.92dy
0.08fe
1-xmn
xo
3the SEM figure of ferroelectric membranc, wherein a～d is respectively the Bi that embodiment 1～embodiment 4 prepares
0.92dy
0.08fe
1-xmn
xo
3the SEM figure of ferroelectric membranc.As can be seen from the figure Bi
0.92dy
0.08fe
1-xmn
xo
3the homogeneous grain size of ferroelectric membranc, film surface is smooth, Bi
0.92dy
0.08fe
0.98mn
0.02o
3ferroelectric membranc densification, pore and defects i.e.cracks content are little.
Fig. 3 is different Mn
2+the Bi preparing under doping
0.92dy
0.08fe
1-xmn
xo
3the specific inductivity figure of ferroelectric membranc, wherein a is according to preparation method of the present invention, does not add C in step 1
4h
6mnO
44H
2the Bi making when O
0.92dy
0.08feO
3the specific inductivity figure of ferroelectric membranc: b～e is respectively the Bi that embodiment 1～embodiment 4 prepares
0.92dy
0.08fe
1-xmn
xo
3the specific inductivity figure of ferroelectric membranc.As can be seen from the figure,, along with the increase of doping, the specific inductivity of film is not monotone increasing, Bi wherein
0.92dy
0.08fe
0.98mn
0.02o
3ferroelectric membranc is within the scope of 1kHz～1MHz test frequency, and its specific inductivity is 260.6～220.69, has good dielectric stability.
Fig. 4 is different Mn
2+the Bi preparing under doping
0.92dy
0.08fe
1-xmn
xo
3the ferroelectric hysteresis loop figure of ferroelectric membranc, wherein a is according to preparation method of the present invention, does not add C in step 1
4h
6mnO
44H
2the Bi making when O
0.92dy
0.08feO
3the ferroelectric hysteresis loop figure of ferroelectric membranc, b～e is respectively Bi prepared by embodiment 1～embodiment 4
0.92dy
0.08fe
1-xmn
xo
3the ferroelectric hysteresis loop figure of ferroelectric membranc.As can be seen from the figure, Bi
0.92dy
0.08fe
0.98mn
0.
02o
3ferroelectric membranc, under the electric field of 833kV/cm, has obtained saturated ferroelectric hysteresis loop, and its remnant polarization is 69.87 μ C/cm
2, coercive field is 330kV/cm.
Embodiment 5
Step 1: in molar ratio for 0.97:0.96:0.08:0.04(is x=0.04) by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Dy (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in mixed solution, obtains even, stable precursor liquid after magnetic agitation 2.5h, and wherein mixed solution is to be 2.5:1 by volume ratio ethylene glycol monomethyl ether and acetic anhydride mix, and in precursor liquid, total concentration of metal ions is 0.35mol/L;
Step 2: first FTO/glass substrate is cleaned, dried, then radiation treatment under UV-light, make FTO/glass substrate surface reach atomic cleanliness degree, adopt again spin-coating method spin coating precursor liquid on FTO/glass substrate to prepare wet film, with the even glue 15s of even glue speed of 3800r/min, after even cementing bundle, at 180 ℃, toast 8min and obtain dry film, then at 540 ℃ of short annealing 8min, obtain Bi
0.92dy
0.08fe
0.96mn
0.04o
3film;
Step 3: treat Bi
0.92dy
0.08fe
0.96mn
0.04o
3after film cooling, then at Bi
0.92dy
0.08fe
0.96mn
0.04o
3on film, repeating step 2, makes Bi
0.92dy
0.08fe
0.96mn
0.04o
3film reaches desired thickness, obtains the Bi of low coercive field
0.92dy
0.08fe
0.96mn
0.04o
3ferroelectric membranc.
Embodiment 6
Step 1: in molar ratio for 0.97:0.975:0.08:0.025(is x=0.025) by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Dy (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in mixed solution, obtains even, stable precursor liquid after magnetic agitation 2.5h, and wherein mixed solution is to be 3.5:1 by volume ratio ethylene glycol monomethyl ether and acetic anhydride mix, and in precursor liquid, total concentration of metal ions is 0.25mol/L;
Step 2: first FTO/glass substrate is cleaned, dried, then radiation treatment under UV-light, make FTO/glass substrate surface reach atomic cleanliness degree, adopt again spin-coating method spin coating precursor liquid on FTO/glass substrate to prepare wet film, with the even glue 13s of even glue speed of 4100r/min, after even cementing bundle, at 210 ℃, toast 12min and obtain dry film, then at 545 ℃ of short annealing 7min, obtain Bi
0.92dy
0.08fe
0.975mn
0.025o
3film;
Step 3:Bi
0.92dy
0.08fe
0.975mn
0.025o
3after film cooling, at Bi
0.92dy
0.08fe
0.975mn
0.025o
3on film, repeating step 2, makes Bi
0.92dy
0.08fe
0.975mn
0.025o
3film reaches desired thickness, obtains the Bi of low coercive field
0.92dy
0.08fe
0.975mn
0.025o
3ferroelectric membranc.
Above-described embodiment 1-6 prepares in the process of precursor liquid in step 1, Bismuth trinitrate (Bi (NO
3)
35H
2o), iron nitrate (Fe (NO
3)
39H
2o), Dysprosium trinitrate (Dy (NO
3)
36H
2and manganous acetate (C O)
4h
6mnO
44H
2o) theoretical molar is than being 0.92:(1-x): 0.08:x, x=0.01～0.05; But in the process of annealing in step 2, Bi
3+have the volatilization loss of part, therefore, the present invention prepares in the process of precursor liquid in step 1, Bismuth trinitrate, iron nitrate, Dysprosium trinitrate and manganous acetate are according to 0.97:(1-x): the mol ratio of 0.08:x is carried out mixed preparing, adopts and adds the method for excessive bismuth ion to compensate Bi in annealing process
3+volatilization, and x=0.01～0.05.
Above said content is in conjunction with concrete preferred implementation further description made for the present invention, it not whole or unique embodiment, the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading specification sheets of the present invention, is claim of the present invention and contains.
Claims (10)
1. the Bi of a low coercive field
0.92dy
0.08fe
1-xmn
xo
3ferroelectric membranc, is characterized in that: its chemical formula is Bi
0.92dy
0.08fe
1-xmn
xo
3, x=0.01～0.05; Under 1kHz frequency, its remnant polarization is 58.27～69.87 μ C/cm
2, coercive field is 318～448kV/cm, specific inductivity is 214.4～260.6.
2. the Bi of low coercive field according to claim 1
0.92dy
0.08fe
1-xmn
xo
3ferroelectric membranc, is characterized in that: it is water chestnut square structure, and space group is R-3m (166), unit cell parameters
grain size is 30～80nm.
3. the Bi of low coercive field according to claim 1 and 2
0.92dy
0.08fe
1-xmn
xo
3ferroelectric membranc, is characterized in that: comprise Bi
0.92dy
0.08fe
0.99mn
0.01o
3ferroelectric membranc, Bi
0.92dy
0.08fe
0.98mn
0.02o
3ferroelectric membranc, Bi
0.92dy
0.08fe
0.97mn
0.03o
3ferroelectric membranc and Bi
0.92dy
0.08fe
0.95mn
0.05o
3ferroelectric membranc;
And Bi
0.92dy
0.08fe
0.99mn
0.01o
3ferroelectric membranc is under the electric field of 583kV/cm, and remnant polarization is 63.62 μ C/cm
2, coercive field is 318kV/cm, in 1kHz～1MHz range of frequency, specific inductivity is 243.1～206.6;
Bi
0.92dy
0.08fe
0.98mn
0.02o
3ferroelectric membranc is under the electric field of 833kv/cm, and remnant polarization is 69.87 μ C/cm
2, coercive field is 330kv/cm, in 1kHz～1MHz range of frequency, specific inductivity is 260.6～220.69;
Bi
0.92dy
0.08fe
0.97mn
0.03o
3ferroelectric membranc is under the electric field of 833kV/cm, and remnant polarization is 58.27 μ C/cm
2, coercive field is 343kV/cm, in 1kHz～1MHz range of frequency, specific inductivity is 214.4～167.01;
Bi
0.92dy
0.08fe
0.95mn
0.05o
3ferroelectric membranc is under the electric field of 917kV/cm, and remnant polarization is 62.88 μ C/cm
2, coercive field is 448kV/cm, in 1kHz～1MHz range of frequency, specific inductivity is 232.3～164.76.
4. the Bi of the low coercive field as described in any one in claim 1-3
0.92dy
0.08fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that, comprises the following steps:
Step 1: be 0.97:(1-x in molar ratio): 0.08:x is by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o, Dy (NO
3)
36H
2o and C
4h
6mnO
44H
2o is dissolved in the mixed solution being mixed by ethylene glycol monomethyl ether and acetic anhydride, stirs, and obtains precursor liquid; Wherein, in precursor liquid, total concentration of metal ions is 0.25～0.35mol/L, x=0.01～0.05;
Step 2: precursor liquid is spin-coated on FTO/glass substrate and prepares wet film, and wet film toasts to obtain dry film after even glue at 180～210 ℃, then 540～550 ℃ of annealing, obtains Bi
0.92dy
0.08fe
1-xmn
xo
3film;
Step 3: treat Bi
0.92d
y0.08fe
1-xmn
xo
3after film cooling, then at Bi
0.92dy
0.08fe
1-xmn
xo
3on film, repeating step 2, makes Bi
0.92dy
0.08fe
1-xmn
xo
3film reaches desired thickness, obtains the Bi of low coercive field
0.92dy
0.08fe
1-xmn
xo
3ferroelectric membranc.
5. the Bi of low coercive field according to claim 4
0.92dy
0.08fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that: in described step 1, in mixed solution, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5～3.5): 1.
6. according to the Bi of the low coercive field described in claim 4 or 5
0.92dy
0.08fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that: x=0.01,0.02,0.03 or 0.05 in described step 1.
7. the Bi of low coercive field according to claim 4
0.92dy
0.08fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that: in described step 2, first FTO/glass substrate is cleaned, dried, then radiation treatment under UV-light, makes FTO/glass substrate surface reach atomic cleanliness degree, finally spin coating precursor liquid again.
8. according to the Bi of the low coercive field described in claim 4 or 7
0.92dy
0.08fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that: the even glue speed in described step 2 when even glue is 3800～4100r/min, and the even glue time is 12～15s.
9. according to the Bi of the low coercive field described in claim 4 or 7
0.92dy
0.08fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that: the baking time in described step 2 after even glue is 8～12min.
10. according to the Bi of the low coercive field described in claim 4 or 7
0.92dy
0.08fe
1-xmn
xo
3the preparation method of ferroelectric membranc, is characterized in that: in described step 2, annealing time is 7～9min.
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| CN104478234A (en) * | 2014-12-11 | 2015-04-01 | 陕西科技大学 | Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn(1-x)CoxFe2O4 composite film and preparation method thereof |
| CN104538139A (en) * | 2014-12-11 | 2015-04-22 | 陕西科技大学 | Bi1-xRExFeO3/CoFe2O4 multiferroic composite membrane and preparation method thereof |
| CN104538140A (en) * | 2014-12-11 | 2015-04-22 | 陕西科技大学 | Multiferroic Bi1-xRExFe0.97-yMn0.03TMyO3/CoFe2O4 composite film and preparation method thereof |
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| CN104538139A (en) * | 2014-12-11 | 2015-04-22 | 陕西科技大学 | Bi1-xRExFeO3/CoFe2O4 multiferroic composite membrane and preparation method thereof |
| CN104538140A (en) * | 2014-12-11 | 2015-04-22 | 陕西科技大学 | Multiferroic Bi1-xRExFe0.97-yMn0.03TMyO3/CoFe2O4 composite film and preparation method thereof |
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